The densities, ρ of pure 1-Hexanol, Benzene and their binary mixture covering the whole composition range have been measured at 303.15 K temperature. Excess molar volumes VmE, partial molar volumes, Vi have been calculated from the ρ data. To obtain correlation coefficients and standard deviations VmE was fitted to Redlich–Kister type function in terms of mole fraction. In the whole range of composition the values of VmE were found to be positive. The positive values of VmE were shown due to depolymerization of the network structures and disrupt their H-bonding and resulting into volume expansion.